Distillation of hydrocarbons with addition of acetone-methyl alcohol



March 947- G. A. DUMMETT ET AL 2,417,355

DISTILLATION OF HYDROCARBONS WITH ADDITION OF ACETONE'METHYL ALCOHOL Filed June 9, 1941 an a nzEjrRa P/c sum /1m? E H.Pfdf' P551100 :IVTRd/MER OZ v Fkrrembye dis/Med //VV//TO?S GEORGE A THONY DUMMETT SIDNEY \IAMIESON RALPH 7 ATTj/PNEYS Patented Mar. 11, 1947 Y t UNITED STATES PATENT OFFICE DI STILLATION OF HYDROCARBONS WITH aggrgr ron E ACETONE-METHYL AL- George Anthony Dummett and Sydney Jamieson Ralph, London, England, assignors to' The Aluminum Plant & Vessel Company Limited, Wandsworth, London, England Application June 9, 1941, Serial No. 397,334 In Great Britain May 10, 1940 2 Claims; (CL 202-42) 1 z This invention relates to the treatment by dislying between that of the constant boiling mixture tillation of complex mixtures, particularly comand another component behave as though the plex mixtures of hydrocarbons or their derivatives, constant boilingl. mixture were a pure component which are not resolvableby ordinary methods of and distil accordingly. It follows, therefore, prodistillation into their individual components. viding that the apparatus and method of opera- The invention is applicable to various complex tion are sufficiently eflicient to separate the mixtures of the nature referred to but is more constant boiling m.xture alone from such mixparticularly concerned with the separation of tures, that it will first be removed at the head of paraflins, naphthenes and unsaturated hydrothe column until virtually all of one of its comcarbons from aromatic hydrocarbons or mixtures D nents i exh sted- D r h s time, h

of the same. temperature remains substantially constant and Non-destructive distillation .processes as at below the boiling point of all of the P present carried out may be divided into those ponents or mixtures of the same and, thereafterwhere aconstant boiling point mixture is formed the temperature rises p y to the normal h or not formed. Processes falling in the former mg point of the remaining mixture and the reclass are termed azeotropic distillatlons, and mainder distils as a s p e e- In cases those falling in the latter class are known as Where more than one constant boilin m xt re is "simple distlllations. In processes falling within formed, these distil in order of their relative the latter class, the boiling point of any mixture v at l t es- For example, in the case of mixtures lies between those of the lowest and highest of e ethyl-alcohol and Water, i excess boiling components. Also, the vapour is always of benzene and ethyll l is P there is richer in the most volatile component than the obtained (1) the ternary Constant boiling liquid with the result'that the composition of the ture of benzene. alcohol and Water at C- mixture is continually being changed. That is to until the water is exhausted, 2 e binary say, as distillation proceeds, the liquid becomes Stant boiling mixture of benzene and alcohol at progressively d ud d of th l w boiling 68.25 C. until the benzene or alcohol is exhausted, ponents in the order of their relative vo'latilities. and (3) benzene or alcohol alone according to Thus, the Engler distillation curve shows a prowhich ever is in excess. Alternatively, if there is gressive rise from o temperature b v that an excess of water present, there is obtained (1) of the boiling point of the most volatile componthe ternary constant boiling mixture of benzene ant to below that of the boiling point of the least alcoholand water at 64.85 C. until the benzene volatile component. Furthermore, in a given disis exhausted, (2) the binary constant boilin mixtillation unit, the composition of the distillate ture of e o ol and water at 78. 5 C. and will depend upon the composition of the liquid (3) pure water at 100C. Inpra ti e. i at th base of the column and n th reflux mediate fractions are formed to a greater or less ratio. It will be appreciated that the higher the degree between the various constant boiling mixconcentration of the most volatile component at s depehdingieh he re at ve volatilities of the the base the higher will be the concentration in constant boiling mixture and the pu e c p the distillate for a given reflux ratio and, the Rents and the freetiehating fi le ey of the higher the reflux ratio, the higher will be the column.

concentration of th t 1 t 1 component, in Distillation processes falling within the class the distillate for a given concentration in the of azeotropic distillations as defined above, are liquid at; th ba of the olu frequently used in order to obtain the selective In processes involving the distillation of mixs t n r components which cannot be s ptures which form constant boiling point mixtures 4 a a n only be separated with reat difof the minimum boiling point type, however, fi u y by o d a y ean For a p a cohol different considerations arise. Firstly, at any and water are ins p e y ple istillat on given pressure there exists a mixture of a definite owing to the formation of a constant boiling composition which boils unchanged at a definite mixture. If, however, benzene or hexane ortriboiling point and in which the vapour phase is chlor-ethylene is added in suitable proportion identical in composition with the liquid phase the water is removed entirely in the ternary conwith which it is in equilibrium, secondly, the stant boiling mixture and the pure alcoholreboiling point of the constant boiling mixture is mains behind. Again, certain paraffins and naphbelow that of any of the components of the mixthenes together form constant boiling mixtures 'ture and, thirdly,--liquids having a composition and are therefore inseparable by simple distlllation. If, however, acetic acid is added, constant boiling mixtures are formed between it and both tion into its components, a substance is added which, under the conditions prevailing during distillation, results in the formation with one component of a mixture of constant boiling point and of constant compositionat a given pressure, 1. e., a true azeotrope. In this way, the isolation of the components of the original mixture becomes possible, Examples of such processes are given above.

Now, according to the present invention, there is provided an improved form of distillation treat-.- ment'which may be termed pseudo-azeotropic" and which is characterized by the addition to the mixture of an entraining agent, which, under the conditions prevailing during distillatiompossesses the property of differentially affecting the relativevolatilities of the components of the mixture without forming a true constant boiling point mixture.

More specifically, the invention may be regarded as consisting in a process of carrying out the distillation of complex mixtures, particularly complex mixtures of hydrocarbons, their derivatives or the like which is characterized by the feature that an entraining agent differing chemically from the complex mixture, is added to the complex mixture so that, under the conditions prevailing during distillation, the relative vapour pressures of the components of the complex mixture are modified in such a-manner that at least one component distils with the entraining agent and leaves behind another component or other components of the complex mixture but without forming true azeotropes during distillation. In this manner, components of a single type in pure or reasonably pure condition or a mixture of components resolvable by simple fractional distillation may be obtained either as a distillate or a residue. Such distillations are characterised by the fact that a greater entraining efficiency as regards the volume of entrainer required to remove a given volume of selected component is obtained by carrying out the distillation under conditions normally considered a ineflicient in either simple or azeotropic distillation.

That is to say, the distillation is rendered more effective as regards the volume of selected component removed by a given volume of entraining agent, by reducing the reflux ratio 'or the volume of entrainer present or both. The entraining agent is preferably added continuously during the distillation and the distillation may be carried out I under reduced or increased pressure.

The nature and the quantity of the entraining agent used will depend upon the characteristics Also, in some instances, the pseudo-azeoti'opic distillation above referred to may be followed by true azeotropic distillation with another entraining agent. In the case of a non-aqueous distillate, the distillate may be treated with water for the separation of its components.

In carrying the invention into effect according to one convenient mode, a mixture having a boiling range of 95 to 125 C. and containing say about 60% of aromatic hydrocarbons mixed with parailins, naphthenes and unsaturated hydrocarbons and inseparable by simple distillation, is distilled with the continuous addition thereto of an entraining agent consisting of about 1.5 to 2 volumes of an acetone-methyl alcohol azeotrope, at the very low reflux ratio of about 1.5 to 1 and at about 56 to 59 C. distilling range and so as to obtain a heads fraction of very high parailln content. Such distillate on mixing with water or salt solution gives an on equal to about 25% of the volume of the original mixture and contains about of paramns and naphthenes. It has been found that such a mixture of entrainer with hydrocarbons which are of similar volatility distils substantially as a mixture of three components, 1. e., entrainer, hydrocarbons of low density and hydrocarbons of high density. The distillation proceeds in' the following order: entrainer plus hydrocarbons of low density without almost no hydrocarbons of high density followed by hydrocarbons of low density plus hydrocarbons of high density. If the relative volatilities of the two types of hydrocarbons were not altered, it would be expected, owing to the wide difference in boiling points, that the distillation would proceed in the following order: almost pure entrainer but with small amounts of hydrocarbons both of low density and of high density to ether, followed by a mixture of the two types of hydrocarbons without appreciable resolution of its components. If, however, the entrainer formed constant boiling mixtures of difierent volatilities with both types of hydrocarbons, it would be expected that the distillation would yield a constant boiling mixture of entrainer and hydrocarbons of low density, followed by a constant boiling mixture of entrainer and hydrocarbons of high density and leave a residue of hydrocarbons of high density or entrainer whichever is in excess.

We have also found that it is not necessary to use pure compounds as entraining agents, but that those ordinarily obtainable of -95% purity are generally suitable. Equally effective are entraining bodies recovered by simple distillation from the decanted water layer, resulting from the mixing referred to above, and which may contain up to 10% of water in the case of the acetone methylalcohol azeotrope, for example.

By first adopting this pseudo-azeotropic method of distillation, it is possible to obtain separations more economically than by using a truly azeotropic distillation process, because a lower reflux ratio with consequent steam economy is obtained, together with in.some cases a more selective separation of those components of the mixture which cause difficulty in other distilla-- tion processes.

That the process of distillation produced according to the present invention is pseudo-azeo tropic in'the sense defined above, is clear from a 1 ture in the presence of an entraining agent with which constant boiling point mixtures of the minimum boiling point type are formed. D is a line indicating the boiling point of the entrainer.

v R will be seen that the temperature remains below that of the boiling point of the entrainer until practically all the entrainer is distilled off when the temperature rises sharply to the normal boiling point of the remaining constituents of the mixture. Such a curve is typical of azeotropic distillation. I

Curve C represents the distillation of the mixture in the presence of another entraining agent of the type referred to in this specification. E is a line indicating the boiling point of this entrainer. It will be seen that the temperature rises steadily from a point above the boiling point of the entrainer. At no point in the curve is there a sudden increase in temperature typical of the complete removal of entrainer. The exhaustion of entrainer in this case is gradual. Such a curve is typical of pseudo-azeotropic distillation, as above defined.

Complex mixtures of the class described are hereby defined as mixtures of liquids which are inseparable by simple distillation, and mixtures of liquids which are separable only with difflculty by simple distillation.

We claim:

1. A process wherein a mixture having a boiling range of 95 to 125 C. and containing about 60% of aromatic hydrocarbons mixed with parafflns, naphthenes and unsaturated hydrocarbons and inseparable by simple distillation, is distilled with the continuous addition thereto of an entraining agent consisting of about 1.5 to 2 volumes of an acetone-methyl alcohol azeotrope, at a low reflux ratio, whereby a head fraction of very high non-aromatic content is obtained.

2. A process according to claim 1 wherein the treatment is followed by true azeotropic distillation with another entraining agent.

GEORGE ANTHONY DUMMETT. SYDNEY JAMIESON REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,212,810 Feld Aug. 27, 1940 2,168,691 Voorhees Aug. 8, 1939 2,085,546 Poelpema June 29,1937 1,919,752 Schmidt et a1. 'July 25, 1933 2,265,220 Sullivan, Jr. Dec. 9, 1941 2,290,636 Deanesly July 21, 1942 2,050,513 Van Peski et a1 Aug. 11, 1936 2,085,287 Bailey June 29, 1937 2,231,241 Bailey Feb. 11, 1941 1,079,004 Golotez Nov. 18, 1913 2,288,126 Dunn et a1 June 30, 1942 2,319,694 Lee et al. May 18, 1943 FOREIGN PATENTS Number Country Date 476,610 British 1937 OTHER REFERENCES 

